JPWO2007122752A1 - Method and apparatus for removing conductive metal oxide thin film - Google Patents

Method and apparatus for removing conductive metal oxide thin film Download PDF

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JPWO2007122752A1
JPWO2007122752A1 JP2008511938A JP2008511938A JPWO2007122752A1 JP WO2007122752 A1 JPWO2007122752 A1 JP WO2007122752A1 JP 2008511938 A JP2008511938 A JP 2008511938A JP 2008511938 A JP2008511938 A JP 2008511938A JP WO2007122752 A1 JPWO2007122752 A1 JP WO2007122752A1
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博之 大工
博之 大工
井上　鉄也
鉄也 井上
孝信 椙本
孝信 椙本
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Abstract

基材（１１）表面の導電性金属酸化物薄膜（１２）に対向して正電極（１３）と第１の負電極（１４）を非接触状態で並列に配置し、さらに、正電極（１３）と第１の負電極（１４）の間に第２の負電極（１７）を、導電性金属酸化物薄膜（１２）の幅方向に複数、接触状態で配置する。そして、導電性金属酸化物薄膜（１２）と電極（１３），（１４），（１７）の間に電解液（１５）を介在させた状態で、導電性金属酸化物薄膜（１２）が、負電極（１４），（１７）を通過後に正電極（１３）を通過するように、基材（１１）を相対移動させることにより、導電性金属酸化物薄膜（１２）を還元反応により除去する。The positive electrode (13) and the first negative electrode (14) are arranged in parallel in a non-contact state so as to face the conductive metal oxide thin film (12) on the surface of the substrate (11), and further, the positive electrode (13 ) And the first negative electrode (14), a plurality of second negative electrodes (17) are arranged in contact with each other in the width direction of the conductive metal oxide thin film (12). And in a state where the electrolytic solution (15) is interposed between the conductive metal oxide thin film (12) and the electrodes (13), (14), (17), the conductive metal oxide thin film (12) The conductive metal oxide thin film (12) is removed by a reduction reaction by relatively moving the substrate (11) so as to pass through the positive electrode (13) after passing through the negative electrodes (14), (17). .

Description

本発明は、例えばスパッタ蒸着などにより基材に形成された導電性金属酸化物薄膜を、再利用が可能なように除去する方法及びその方法を実施する装置に関するものである。   The present invention relates to a method for removing a conductive metal oxide thin film formed on a substrate by, for example, sputter deposition so that it can be reused, and an apparatus for carrying out the method.

例えばＩＴＯ（インジウムとスズの酸化物で、透明導電性を有する膜）を形成した高機能ガラス基板は、光学的性能（透過率等）や機械的性能（平坦度等）に優れており、例えばフラットパネルディスプレイに用いられる。しかしながら、この高機能ガラス基板は高価であるため、その表面に形成するＩＴＯが品質管理基準を満足しない場合には、そのＩＴＯを除去して再利用することで、コストの低減を図っている。   For example, a high-performance glass substrate on which ITO (a film having transparent conductivity with an oxide of indium and tin) is excellent in optical performance (such as transmittance) and mechanical performance (such as flatness). Used for flat panel displays. However, since this high-performance glass substrate is expensive, when the ITO formed on the surface does not satisfy the quality control standard, the ITO is removed and reused to reduce the cost.

このＩＴＯなどの導電性金属酸化物薄膜を除去する方法として、機械的擦過により除去する方法や、化学エッチングにより除去する方法がある。このうち前者の方法は、図１１に示すように、被加工物１の表面に形成した導電性金属酸化物薄膜１ａを研摩ブラシ２により擦過することで除去するものである。   As a method of removing the conductive metal oxide thin film such as ITO, there are a method of removing by mechanical abrasion and a method of removing by chemical etching. The former method is to remove the conductive metal oxide thin film 1 a formed on the surface of the workpiece 1 by rubbing with a polishing brush 2 as shown in FIG. 11.

また、後者の方法は、図１２に示すように、導電性金属酸化物薄膜１ａを化学反応的に溶解させる化学液３に被加工物１を浸漬することで、その表面に形成した導電性金属酸化物薄膜１ａを除去するものである（例えば特許文献１，２）。
日本特開平６−３２１５８１号公報 日本特開平９−８６９６８号公報 In the latter method, as shown in FIG. 12, the conductive metal formed on the surface of the workpiece 1 is immersed in a chemical solution 3 that chemically dissolves the conductive metal oxide thin film 1a. The oxide thin film 1a is removed (for example, Patent Documents 1 and 2).
Japanese Unexamined Patent Publication No. 6-321581 Japanese Unexamined Patent Publication No. 9-86968

しかしながら、機械的擦過によって除去する方法は、研摩ブラシを擦りつけることから、被加工物の表面に擦過痕（疵）や応力変形を生じさせる場合がある。擦過痕が生じた場合、再利用ができなくなる。また、対象とする被加工物がフラットパネルディスプレイの場合、ガラス基板のガラス厚みが０．５mm程度であるため、接触方式の機械的擦過では破損する可能性がある。従って、微妙なブラシの圧力調整が必要で、完全に剥離するためには長時間を要する。   However, since the method of removing by mechanical rubbing rubs the polishing brush, there are cases where rubbing marks (wrinkles) and stress deformation occur on the surface of the workpiece. When scratch marks are generated, it cannot be reused. Moreover, when the object to be processed is a flat panel display, the glass thickness of the glass substrate is about 0.5 mm. Therefore, delicate pressure adjustment of the brush is necessary, and it takes a long time to completely peel off.

一方、化学エッチングによって除去する方法は、強酸や強アルカリの化学液を使用するので、基板表面に化学的応力が発生し、基板表面に変質層を生じさせる場合がある。また、取扱いに十分な注意を払う必要があり、作業性が悪くなるばかりでなく、使用後の電解液を廃液処理する必要がある。また、希少金属の回収には、別途抽出作業を必要とするために非常に不経済である。   On the other hand, the method of removing by chemical etching uses a strong acid or strong alkali chemical solution, so that chemical stress is generated on the surface of the substrate and an altered layer may be formed on the surface of the substrate. In addition, it is necessary to pay sufficient attention to handling, not only the workability is deteriorated, but also the electrolytic solution after use needs to be treated as a waste solution. Also, the collection of rare metals is very uneconomical because it requires a separate extraction operation.

本発明が解決しようとする問題点は、機械的擦過による方法では、擦過痕や応力変形が生じて基材を再利用できなくなり、また、ブラシの微妙な圧力調整が必要で完全剥離に長時間を要するという点、化学エッチングによる方法では、基板表面に変質層を生じさせる場合があり、また作業性が悪くなるばかりか、使用後の電解液を廃液処理する必要があり、しかも、希少金属の回収に別途抽出作業が必要で、不経済であるという点である。   The problems to be solved by the present invention are that mechanical scratching causes scratch marks and stress deformation, making it impossible to reuse the substrate, and delicate pressure adjustment of the brush is necessary, and complete peeling takes a long time. In the method using chemical etching, a deteriorated layer may be formed on the surface of the substrate, and workability is deteriorated. In addition, it is necessary to dispose the used electrolytic solution as a waste liquid. This requires that a separate extraction operation is required for collection, which is uneconomical.

本発明の導電性金属酸化物薄膜の除去方法は、
できるだけ基材に擦過痕や応力変形などを残さず、かつ、強酸や強アルカリの化学液を使用しないで、基材の導電性金属酸化物薄膜を基材の端部まで、僅かな残留膜もなく、効率良く除去するために、
基材の表面に形成された導電性金属酸化物薄膜に対向すべく、
正電極と第１の負電極を非接触状態で並列に配置すると共に、前記第１の負電極の前段又は後段、或いは、前段及び後段に、第２の負電極を前記導電性金属酸化物薄膜の幅方向に複数、接触状態で配置した後、
これらの正電極、第１，第２の負電極と前記導電性金属酸化物薄膜間に電解液を介在させた状態で、
前記正電極、第１，第２の負電極に電圧を印加して、
前記正電極、第１，第２の負電極と基材の表面に形成された導電性金属酸化物薄膜とを、導電性金属酸化物薄膜が第１の負電極、第２の負電極を通過後に正電極を通過するように相対移動させることで、前記基材表面の導電性金属酸化物薄膜を還元反応により除去することを最も主要な特徴としている。The method for removing the conductive metal oxide thin film of the present invention comprises:
Keep the conductive metal oxide thin film of the base material to the edge of the base material and leave a slight residual film without leaving scratch marks or stress deformation on the base material as much as possible, and without using strong acid or strong alkali chemicals. To remove it efficiently,
To face the conductive metal oxide thin film formed on the surface of the substrate,
The positive electrode and the first negative electrode are arranged in parallel in a non-contact state, and the second negative electrode is placed on the conductive metal oxide thin film before or after the first negative electrode, or before and after the first negative electrode. After arranging a plurality of contacts in the width direction,
In a state where an electrolyte is interposed between the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film,
Apply voltage to the positive electrode, the first and second negative electrodes,
The conductive metal oxide thin film passes through the first negative electrode and the second negative electrode through the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film formed on the surface of the substrate. The main feature is that the conductive metal oxide thin film on the surface of the base material is removed by a reduction reaction by relative movement so as to pass through the positive electrode later.

この本発明の導電性金属酸化物薄膜の除去方法では、正電極と第１の負電極の間に、第２の負電極を前記導電性金属酸化物薄膜の幅方向に接触状態で複数配置することにより、基材の表面に形成された導電性金属酸化物薄膜を端部まで除去することができる。   In the method for removing a conductive metal oxide thin film of the present invention, a plurality of second negative electrodes are arranged in contact with each other in the width direction of the conductive metal oxide thin film between the positive electrode and the first negative electrode. Thus, the conductive metal oxide thin film formed on the surface of the substrate can be removed to the end.

前記本発明の導電性金属酸化物薄膜の除去方法は、前記正電極と第１の負電極として、導電性金属酸化物薄膜の幅よりも狭幅のものを千鳥状に配置したものを使用しても良い。   In the method for removing a conductive metal oxide thin film according to the present invention, the positive electrode and the first negative electrode are arranged in a staggered manner with a width narrower than the width of the conductive metal oxide thin film. May be.

前記本発明の導電性金属酸化物薄膜の除去方法においては、抵抗率が１０2Ω・cmから１０6Ω・cmの電解液を使用することで、基材表面に形成された導電性金属酸化物薄膜を効率良く除去することが可能になる。In the method for removing a conductive metal oxide thin film of the present invention, the conductive metal oxide formed on the surface of the substrate is used by using an electrolyte having a resistivity of 10 2 Ω · cm to 10 6 Ω · cm. It is possible to efficiently remove the physical thin film.

本発明の導電性金属酸化物薄膜の除去方法は、
基材の表面に形成された導電性金属酸化物薄膜に対向すべく非接触状態で並列に配置された正電極及び第１の負電極と、
前記第１の負電極の前段又は後段、或いは、前段及び後段に、前記導電性金属酸化物薄膜に対向すべく導電性金属酸化物薄膜の幅方向に接触状態で複数配置された第２の負電極と、
これら正電極、第１，第２の負電極と前記基材の表面に形成された導電性金属酸化物薄膜間に電解液を供給する手段、或いは、前記の正電極、第１，第２の負電極と基材を電解液内に浸漬すべく電解液を貯留する電解液槽と、
これらの正電極と第１，第２の負電極に電圧を印加する電源と、
前記正電極、第１，第２の負電極と基材の表面に形成された導電性金属酸化物薄膜とを、導電性金属酸化物薄膜が第１の負電極、第２の負電極を通過後に正電極を通過するように相対移動させる移動機構を備えた本発明装置を使用することによって実施できる。The method for removing the conductive metal oxide thin film of the present invention comprises:
A positive electrode and a first negative electrode arranged in parallel in a non-contact state to face the conductive metal oxide thin film formed on the surface of the substrate;
A plurality of second negative electrodes arranged in contact with each other in the width direction of the conductive metal oxide thin film so as to face the conductive metal oxide thin film before or after the first negative electrode, or before and after the first negative electrode. Electrodes,
Means for supplying an electrolytic solution between the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film formed on the surface of the substrate, or the positive electrode, the first and second electrodes An electrolytic bath for storing the electrolytic solution so as to immerse the negative electrode and the substrate in the electrolytic solution;
A power source for applying a voltage to the positive electrode and the first and second negative electrodes;
The conductive metal oxide thin film passes through the first negative electrode and the second negative electrode through the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film formed on the surface of the substrate. It can be implemented by using the device of the present invention provided with a moving mechanism that moves relative to pass through the positive electrode later.

前記本発明の導電性金属酸化物薄膜の除去装置は、前記正電極と第１の負電極を、導電性金属酸化物薄膜の幅よりも狭幅のものを千鳥状に、或いは、導電性金属酸化物薄膜の幅よりも狭幅の湾曲状のものを連続して配置したものとしても良い。   The apparatus for removing a conductive metal oxide thin film according to the present invention is characterized in that the positive electrode and the first negative electrode are staggered or narrower than the width of the conductive metal oxide thin film. A curved shape narrower than the width of the oxide thin film may be continuously arranged.

本発明では、
1) 正電極と、第１の負電極の前段又は後段、或いは、前段及び後段に第２の負電極を、前記導電性金属酸化物薄膜の幅方向に接触状態で複数配置することで、基材に擦過痕や応力変形を残さずに、効率良く、導電性金属酸化物薄膜のみを除去することができる。
2) 前記正電極と第１の負電極を、導電性金属酸化物薄膜の幅方向に、導電性金属酸化物薄膜の幅よりも狭幅のものを千鳥状、或いは、導電性金属酸化物薄膜の幅よりも狭幅の湾曲状のものを連続して配置することで、基材の表面に形成された導電性金属酸化物薄膜を端部まで効率良く除去することができる。In the present invention,
1) By arranging a plurality of second negative electrodes in contact with each other in the width direction of the conductive metal oxide thin film, a positive electrode and a first negative electrode before or after the first negative electrode, or before and after the first negative electrode, Only the conductive metal oxide thin film can be efficiently removed without leaving scratch marks or stress deformation on the material.
2) The positive electrode and the first negative electrode are staggered in the width direction of the conductive metal oxide thin film or narrower than the width of the conductive metal oxide thin film, or the conductive metal oxide thin film By continuously disposing the curved shape narrower than the width, the conductive metal oxide thin film formed on the surface of the base material can be efficiently removed to the end.

また、強酸や強アルカリの化学液を使用しないので、環境負荷も低減でき、基材を始めとする希少金属などの資源サイクルも可能になって、経済的にも有利である。   Further, since no strong acid or strong alkali chemical solution is used, the environmental load can be reduced, and resource cycles such as rare metals such as base materials can be realized, which is economically advantageous.

（ａ）は本発明の基本原理を説明する図、（ｂ）は問題点を説明する図である。(A) is a figure explaining the basic principle of this invention, (b) is a figure explaining a problem. 本発明の第１の例を説明する概略図で、（ａ）は側面から見た図、（ｂ）は平面から見た図である。BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic explaining the 1st example of this invention, (a) is the figure seen from the side surface, (b) is the figure seen from the plane. 本発明の第１の例における移動速度と電解還元電流の関係を示した図である。It is the figure which showed the relationship between the moving speed and the electrolytic reduction current in the 1st example of this invention. 移動速度に対して電解還元電流が大きすぎた場合の還元状態を説明する図である。It is a figure explaining the reduction state when the electrolytic reduction current is too large with respect to the moving speed. 本発明の第２の例を説明する平面方向から見た概略図である。It is the schematic seen from the plane direction explaining the 2nd example of the present invention. 図５に示した本発明の第２の例において、導電性酸化物薄膜の最終端部が還元できることを説明する図である。In the 2nd example of this invention shown in FIG. 5, it is a figure explaining that the last edge part of a conductive oxide thin film can be reduce | restored. 本発明の第３の例を説明する平面方向から見た概略図である。It is the schematic seen from the plane direction explaining the 3rd example of the present invention. 図７に示した本発明の第３の例において、導電性酸化物薄膜の最終端部が還元できることを説明する図である。FIG. 8 is a diagram illustrating that the final end portion of the conductive oxide thin film can be reduced in the third example of the present invention shown in FIG. 7. 本発明の第４の例を説明する側面方向から見た概略図である。It is the schematic seen from the side surface explaining the 4th example of the present invention. 本発明により導電性金属酸化物薄膜を電解還元処理した後の回収装置の一例を示した図である。It is the figure which showed an example of the collection | recovery apparatus after carrying out the electrolytic reduction process of the electroconductive metal oxide thin film by this invention. 機械的擦過により金属薄膜を除去する方法について説明する図である。It is a figure explaining the method of removing a metal thin film by mechanical abrasion. 化学エッチングにより金属薄膜を除去する方法について説明する図である。It is a figure explaining the method of removing a metal thin film by chemical etching.

符号の説明Explanation of symbols

１１ 基材
１２ 導電性金属酸化物薄膜
１２ａ 導電性金属
１３ 正電極
１４ 第１の負電極
１５ 電解液
１６ 電源
１７ 第２の負電極DESCRIPTION OF SYMBOLS 11 Base material 12 Conductive metal oxide thin film 12a Conductive metal 13 Positive electrode 14 1st negative electrode 15 Electrolytic solution 16 Power supply 17 2nd negative electrode

本発明は、基材の導電性金属酸化物薄膜を、基材の端部まで僅かな残留膜もなく効率良く除去するという目的を、非接触による電解溶出で付着力を弱めた後に、基材に形成された導電性金属を除去するに際し、正電極と第１の負電極の間に、第２の負電極を前記導電性金属酸化物薄膜の幅方向に接触状態で複数配置することによって実現した。   The purpose of the present invention is to remove the conductive metal oxide thin film of the base material efficiently without a slight residual film up to the end of the base material, after weakening the adhesive force by non-contact electrolytic elution. When removing the conductive metal formed on the substrate, a plurality of second negative electrodes are arranged in contact with each other in the width direction of the conductive metal oxide thin film between the positive electrode and the first negative electrode. did.

以下、本発明の基本原理を、図１を用いて説明した後、本発明を実施するための最良の形態と共に各種の形態を図２〜図１０を用いて詳細に説明する。   Hereinafter, the basic principle of the present invention will be described with reference to FIG. 1, and various embodiments will be described in detail with reference to FIGS. 2 to 10 together with the best mode for carrying out the present invention.

本発明は、できるだけ基材への疵や応力変形などを残さない加工法で、かつ、強酸や強アルカリを使用しない導電性金属酸化物薄膜の除去方法である。
つまり、本発明では、図１（ａ）のように、表面に導電性金属酸化物薄膜１２を形成した絶縁物や導電物などの基材１１の上方に、たとえば前記導電性金属酸化物薄膜１２の幅よりも広幅の正電極１３と負電極（以下、第１の負電極という）１４を非接触状態で並列に配置する。The present invention is a processing method that leaves as little wrinkles and stress deformation on a substrate as possible, and a method for removing a conductive metal oxide thin film that does not use strong acid or strong alkali.
That is, in the present invention, as shown in FIG. 1A, for example, the conductive metal oxide thin film 12 is formed above the base material 11 such as an insulator or a conductive material on which the conductive metal oxide thin film 12 is formed. A positive electrode 13 and a negative electrode (hereinafter referred to as a first negative electrode) 14 having a width wider than that of the first electrode 14 are arranged in parallel in a non-contact state.

そして、たとえば電解液槽内の電解液１５に、前記の正電極１３と第１の負電極１４を浸漬配置し、電源１６から直流電圧或いはパルス電圧を印加して、導電性金属酸化物薄膜１２が第１の負電極１４を通過した後に正電極１３を通過するように、基材１１を移動させるのである。   Then, for example, the positive electrode 13 and the first negative electrode 14 are immersed in the electrolytic solution 15 in the electrolytic bath, and a DC voltage or a pulse voltage is applied from the power source 16 to thereby form the conductive metal oxide thin film 12. Then, the base material 11 is moved so as to pass through the positive electrode 13 after passing through the first negative electrode 14.

このようにすることで、電源１６（＋）−正電極１３−電解液１５−導電性金属酸化物薄膜１２−電解液１５−第１の負電極１４−電源１６（−）の閉回路が形成され、正電極１３近傍の導電性金属酸化物薄膜１２の表面からＨ2の微細気泡が発生する。By doing in this way, the closed circuit of power supply 16 (+)-positive electrode 13-electrolytic solution 15-conductive metal oxide thin film 12-electrolytic solution 15-first negative electrode 14-power supply 16 (-) is formed. Then, H 2 microbubbles are generated from the surface of the conductive metal oxide thin film 12 in the vicinity of the positive electrode 13.

このとき、正電極１３近傍の導電性金属酸化物薄膜１２の表面に発生するＨ2が還元剤となり、導電性金属酸化物薄膜１２中のＯ2を取り除く作用が生じる。さらに、このＨ2の発生は導電性金属酸化物薄膜１２の界面で生じることから効率の良い還元反応が生じる。At this time, H 2 generated on the surface of the conductive metal oxide thin film 12 in the vicinity of the positive electrode 13 serves as a reducing agent, and an action of removing O 2 in the conductive metal oxide thin film 12 occurs. Furthermore, since the generation of H 2 occurs at the interface of the conductive metal oxide thin film 12, an efficient reduction reaction occurs.

Ｏ2による結合が無くなった導電性金属酸化物薄膜１２は金属元素だけとなり、基材１１の表面に結合力が弱まった状態で存在するようになる。基材１１との結合が弱まった導電性金属１２ａは、弱い応力で擦過する例えば回転スポンジ体などの柔軟性体によって基材１１から確実に除去される。The conductive metal oxide thin film 12 that is no longer bonded by O 2 contains only a metal element, and exists on the surface of the base material 11 in a state where the bonding force is weakened. The conductive metal 12a whose bond with the base material 11 has been weakened is reliably removed from the base material 11 by a flexible material such as a rotating sponge body that is rubbed with a weak stress.

しかしながら、図１（ａ）のように、正電極１３及び第１の負電極１４が、導電性金属酸化物薄膜１２と非接触の状態であると、前記正電極１３及び第１の負電極１４と導電性金属酸化物薄膜１２間に介在する電解液１５が抵抗となって、効率良く導電性金属酸化物薄膜１２を除去できない。逆に、正電極１３及び第１の負電極１４が導電性金属酸化物薄膜１２と接触の状態であると、両電極１３，１４に大量の気泡（水素及び酸素）が付着し、電極１３，１４の電流密度が低下することで導電性金属酸化物薄膜１２の除去効果が低下し、完全に除去することができない。   However, as shown in FIG. 1A, when the positive electrode 13 and the first negative electrode 14 are not in contact with the conductive metal oxide thin film 12, the positive electrode 13 and the first negative electrode 14 are provided. The electrolytic solution 15 interposed between the conductive metal oxide thin film 12 becomes a resistance, and the conductive metal oxide thin film 12 cannot be removed efficiently. On the contrary, when the positive electrode 13 and the first negative electrode 14 are in contact with the conductive metal oxide thin film 12, a large amount of bubbles (hydrogen and oxygen) adhere to both the electrodes 13, 14, and the electrodes 13, When the current density of 14 is lowered, the removal effect of the conductive metal oxide thin film 12 is lowered and cannot be completely removed.

また、図１（ａ）のような電極配置では、第１の負電極１４が導電性金属酸化物薄膜１２の最終端部を通過すると、導電性金属酸化物薄膜１２と第１の負電極１４との間隔が離れていくので、導電性金属酸化物薄膜１２に流れる電流量が急激に低下して、還元に必要な電流が流れなくなる。   Further, in the electrode arrangement as shown in FIG. 1A, when the first negative electrode 14 passes the final end of the conductive metal oxide thin film 12, the conductive metal oxide thin film 12 and the first negative electrode 14. , The amount of current flowing through the conductive metal oxide thin film 12 is abruptly reduced, and the current necessary for reduction does not flow.

つまり、図１（ａ）のような電極配置では、導電性金属酸化物薄膜１２の後端部は、図１（ｂ）に示すように、正電極１３と第１の負電極１４間の間隔Ｘだけ還元されないことになる。また、図１（ａ）のような電極配置では、第１の負電極１４と導電性金属酸化物薄膜１２間に介在する電解液１５の抵抗が存在するため、還元に必要な電流を流す電圧が大きくなる。   That is, in the electrode arrangement as shown in FIG. 1A, the rear end portion of the conductive metal oxide thin film 12 has a gap between the positive electrode 13 and the first negative electrode 14 as shown in FIG. Only X will not be reduced. Further, in the electrode arrangement as shown in FIG. 1A, since there is a resistance of the electrolytic solution 15 interposed between the first negative electrode 14 and the conductive metal oxide thin film 12, a voltage for passing a current necessary for reduction is provided. Becomes larger.

そこで、本発明では、例えば電解液槽内の電解液１５に浸漬する正電極１３と第１の負電極１４の間に、図２に示すように、第２の負電極１７を導電性金属酸化物薄膜１２の幅方向に複数個、接触状態で配置するのである。なお、図２中の１８は第２の負電極１７を導電性金属酸化物薄膜１２に押し付けるばね等の押し付け機構である。   Therefore, in the present invention, for example, between the positive electrode 13 immersed in the electrolytic solution 15 in the electrolytic solution tank and the first negative electrode 14, the second negative electrode 17 is electrically conductive metal oxidized as shown in FIG. A plurality of physical thin films 12 are arranged in contact with each other in the width direction. 2 denotes a pressing mechanism such as a spring that presses the second negative electrode 17 against the conductive metal oxide thin film 12.

本発明では、前記第２の負電極１７同士の間隔Ｌは、正電極１３と第１の負電極１４間の間隔Ｘ（mm）以上で、正電極１３と第１の負電極１４間の間隔Ｘ（mm）の１０倍以下とすることが望ましい（図２（ｂ）参照）。   In the present invention, the interval L between the second negative electrodes 17 is not less than the interval X (mm) between the positive electrode 13 and the first negative electrode 14 and the interval between the positive electrode 13 and the first negative electrode 14. It is desirable to make it 10 times or less of X (mm) (see FIG. 2B).

第２の負電極１７同士の間隔Ｌが、正電極１３と第１の負電極１４間の間隔Ｘ（mm）未満であると、第２の負電極１４に大量の気泡（水素）が付着して電極の電流密度が低下する（導電性金属酸化物薄膜１２の除去漏れ（むら）ができる）からである。反対に正電極１３と第１の負電極１４間の間隔Ｘ（mm）の１０倍を超えると、還元電流の効率が低下し、接触電極を付加することによる効果が低下するからである。   When the interval L between the second negative electrodes 17 is less than the interval X (mm) between the positive electrode 13 and the first negative electrode 14, a large amount of bubbles (hydrogen) adhere to the second negative electrode 14. This is because the current density of the electrode decreases (the removal leakage (unevenness) of the conductive metal oxide thin film 12 can occur). Conversely, if the distance X (mm) between the positive electrode 13 and the first negative electrode 14 exceeds 10 times, the efficiency of the reduction current is reduced, and the effect of adding the contact electrode is reduced.

また、本発明では、還元に必要な電流値Ｉ（A）は、正電極１３、第１，第２の負電極１４，１７と基材１１との相対移動速度（cm／分）と正電極１３の電極幅Ｙ（cm）を乗算した値の０．００３倍以上で、０．０１倍以下とすることが望ましい（図３参照）。   In the present invention, the current value I (A) required for reduction is determined by the relative movement speed (cm / min) between the positive electrode 13, the first and second negative electrodes 14, 17 and the substrate 11, and the positive electrode. It is desirable that the value be 0.003 times or more and 0.01 times or less the value obtained by multiplying the electrode width Y (cm) of 13 (see FIG. 3).

前記０．００３倍未満では、還元が不足して導電性金属酸化物薄膜１２の表面部しか還元除去できないからである。   This is because if it is less than 0.003 times, the reduction is insufficient and only the surface portion of the conductive metal oxide thin film 12 can be reduced and removed.

また、０．０１倍を超えると、導電性金属酸化物薄膜１２が過剰に還元されて導電性金属酸化物薄膜１２が還元と同時に基材１１から剥離し、正電極１３と導電性金属酸化物薄膜１２の間隔が離れて導電性金属酸化物薄膜１２に流れる電流が急激に低下し、還元に必要な電流が流れにくくなるためである。   On the other hand, if it exceeds 0.01 times, the conductive metal oxide thin film 12 is excessively reduced and the conductive metal oxide thin film 12 is peeled off from the substrate 11 simultaneously with the reduction, and the positive electrode 13 and the conductive metal oxide are removed. This is because the current flowing through the conductive metal oxide thin film 12 decreases rapidly due to the separation of the thin film 12, and it becomes difficult for the current necessary for reduction to flow.

そして、剥離部分を正電極１３が通過すると、再び還元できるようになり、これが繰り返されて、図４に示したように、縞状に還元されない部分が残るのである。   Then, when the positive electrode 13 passes through the peeled portion, it can be reduced again, and this is repeated, and as shown in FIG. 4, a portion that is not reduced in a striped shape remains.

このような構成の本発明によれば、第１の負電極１４の前段又は後段、或いは、前段及び後段に設けられた第２の負電極１７により、前記第１の負電極１４と導電性金属酸化物薄膜１２間に介在する電解液１５との抵抗がなくなり、導電性金属酸化物薄膜１２の除去効率が良くなるとともに、還元に必要な電流を低くすることができる。また、第２の負電極１７同士を間隔Ｌで複数配置することで、電極１３，１４，１７に大量の気泡が付着することによる電極の電流密度の低下を低減することができる。   According to the present invention having such a configuration, the first negative electrode 14 and the conductive metal are formed by the second negative electrode 17 provided at the front stage or the rear stage of the first negative electrode 14 or at the front stage and the rear stage. The resistance with the electrolyte solution 15 interposed between the oxide thin films 12 is eliminated, the removal efficiency of the conductive metal oxide thin film 12 is improved, and the current required for reduction can be reduced. In addition, by arranging a plurality of second negative electrodes 17 at intervals L, it is possible to reduce a decrease in electrode current density due to a large amount of bubbles adhering to the electrodes 13, 14, and 17.

また、図２に示した本発明に代えて、図５に示した構成としても良い。
図５に示した例は、図２に示した正電極１３と第１の負電極１４を、導電性金属酸化物薄膜１２の幅方向に、導電性金属酸化物薄膜１２の幅よりも狭幅のものを千鳥状に並列に配置したものである。Further, the configuration shown in FIG. 5 may be used instead of the present invention shown in FIG.
In the example shown in FIG. 5, the positive electrode 13 and the first negative electrode 14 shown in FIG. 2 are narrower than the width of the conductive metal oxide thin film 12 in the width direction of the conductive metal oxide thin film 12. Are arranged in a staggered pattern in parallel.

正電極１３と第１の負電極１４を千鳥状に配置することで、図６に示すように、隣り合う正電極１３と第１の負電極１４間（図６にハッチングで示す部分）で電解還元が生じ、導電性金属酸化物薄膜１２の最終端部でも還元できるようになる。   By arranging the positive electrode 13 and the first negative electrode 14 in a staggered manner, as shown in FIG. 6, electrolysis is performed between the adjacent positive electrode 13 and the first negative electrode 14 (the portion indicated by hatching in FIG. 6). Reduction occurs and the final end portion of the conductive metal oxide thin film 12 can be reduced.

また、図５に示した例に代えて、図７のように、正電極１３と第１の負電極１４を、導電性金属酸化物薄膜１２の幅方向に、導電性金属酸化物薄膜１２の幅よりも狭幅の湾曲状のものを連続して配置したものとしても、図８にハッチングで示す部分で電解還元が生じ、同様の作用効果を得ることができる。   Further, instead of the example shown in FIG. 5, the positive electrode 13 and the first negative electrode 14 are arranged in the width direction of the conductive metal oxide thin film 12 as shown in FIG. 7. Even if the curved shape narrower than the width is continuously arranged, electrolytic reduction occurs in the portion indicated by hatching in FIG. 8, and the same effect can be obtained.

さらに、図９に示したように、前記第２の負電極１７を、導電性金属酸化物薄膜１２の最終端部に接触状態で配置し、たとえば基材１１（導電性金属酸化物薄膜１２）の移動時、第２の負電極１７を基材１１と同調移動させて導電性金属酸化物薄膜１２の最終端部との相対位置関係を維持するようにしても良い。   Further, as shown in FIG. 9, the second negative electrode 17 is disposed in contact with the final end of the conductive metal oxide thin film 12, for example, the base material 11 (conductive metal oxide thin film 12). During the movement, the second negative electrode 17 may be moved in synchronization with the base material 11 to maintain the relative positional relationship with the final end portion of the conductive metal oxide thin film 12.

以上の本発明では、導電性金属酸化物薄膜１２は電解還元処理した後は、金属固体として微粒子化（０．１μm以下）しているので、たとえば図１０に示すように、水流ジェット２０により還元金属を剥離すれば良い。なお、図１０では、補助として柔軟性材２１による機械的剥離を併用するものを示している。   In the present invention described above, since the conductive metal oxide thin film 12 is finely divided (0.1 μm or less) as a metal solid after the electrolytic reduction treatment, for example, as shown in FIG. What is necessary is just to peel a metal. In addition, in FIG. 10, what uses together mechanical peeling by the flexible material 21 as assistance is shown.

そして、その後は、電解液とともに除去した還元金属を、電解液捕集パン２２を介して回収タンク２３に溜め、マイクロバブル発生器２４によってマイクロバブルを混入する。これにより、マイクロバブルが核となって金属微粒子がクラスタ化し、フィルタで回収できるようになるので、フィルタ２５を通して還元金属を回収する。なお、図１０中の２６はポンプを示す。   After that, the reduced metal removed together with the electrolytic solution is accumulated in the recovery tank 23 via the electrolytic solution collecting pan 22, and microbubbles are mixed by the microbubble generator 24. As a result, the metal bubbles are clustered using the microbubbles as a nucleus and can be collected by the filter. In addition, 26 in FIG. 10 shows a pump.

以上の説明のように、本発明は、一般に行われている、被加工物に正電圧を印加する電解溶出除去反応ではなく、被加工物に負の電圧を印加する特徴的な加工法である。
なお、ここでの電解反応は導電性金属酸化物薄膜界面のごく微量な領域にＨ2の発生を生じさせるもので良いため、電流はほとんど必要としない。As described above, the present invention is a characteristic processing method for applying a negative voltage to a workpiece, not a general electrolytic elution removal reaction for applying a positive voltage to the workpiece, as described above. .
The electrolytic reaction here may generate H2 in a very small region at the interface of the conductive metal oxide thin film, so that almost no current is required.

従って、使用する電解液１５は、一般に用いられる中性塩溶液、または水道水や河川水や、水道水や河川水等に中性塩溶液を混合したものが利用可能であるが、正電極１３、負電極１４ともに基材１１とは非接触の場合は、好ましくは、前述のように抵抗率が１０2Ω・cmから１０6Ω・cm、より好ましくは１０3Ω・cmから１０4Ω・cmに調整されたものが良い。Therefore, as the electrolyte 15 to be used, a neutral salt solution that is generally used, or a mixture of a neutral salt solution in tap water, river water, tap water, river water, or the like can be used. When the negative electrode 14 is not in contact with the substrate 11, the resistivity is preferably 10 2 Ω · cm to 10 6 Ω · cm, more preferably 10 3 Ω · cm to 10 4 Ω, as described above.・ Adjusted to cm.

本発明では、正電極１３、第１の負電極１４が基材１１とは非接触の場合、抵抗率が１０2Ω・cm未満の導電性の高い電解液１５では、両電極１３，１４間に印加された電圧が、導電性金属酸化物薄膜１２を通さず、前記両電極１３，１４間で電解液１５を通して導通状態となるため、導電性金属酸化物薄膜１２の除去効率が低下するからである。また、抵抗率が１０6Ω・cmを超えると高電圧を印加する必要があり、経済上好ましくないからである。In the present invention, when the positive electrode 13 and the first negative electrode 14 are not in contact with the base material 11, in the highly conductive electrolyte 15 having a resistivity of less than 10 2 Ω · cm, between the electrodes 13 and 14. Since the voltage applied to the conductive metal oxide thin film 12 does not pass through the electrolyte solution 15 between the electrodes 13 and 14, the removal efficiency of the conductive metal oxide thin film 12 decreases. It is. Further, if the resistivity exceeds 10 6 Ω · cm, it is necessary to apply a high voltage, which is economically undesirable.

このように本発明では、抵抗率の比較的高い電解液１５が適していることから、従来、電解液１５としては好ましくなかった、水道水や河川水等を用いることができ、経済性および安全性の面においても優れている。   Thus, in the present invention, since the electrolytic solution 15 having a relatively high resistivity is suitable, tap water, river water, and the like, which are not preferable as the electrolytic solution 15 conventionally, can be used. Also excellent in terms of sex.

ちなみに、電解液として水道水を使用し、ガラス基板上に膜厚が１５００×１０−10mのＩＴＯを形成した１００mm×１００mmの被加工物を、図２に示したように、前記電解液中に浸漬した。Incidentally, as shown in FIG. 2, a work piece of 100 mm × 100 mm in which tap water is used as an electrolytic solution and ITO having a film thickness of 1500 × 10 −10 m is formed on a glass substrate is formed in the electrolytic solution as shown in FIG. Soaked in.

同じく電解液中にＣｕ製の正電極と第１，第２の負電極（正電極と第１の負電極の幅は共に１２０mmで、両電極間の間隔Ｘは１０mm。また、第２の負電極は２個。）を浸漬した。   Similarly, a positive electrode made of Cu and first and second negative electrodes in the electrolytic solution (the width of the positive electrode and the first negative electrode are both 120 mm, and the distance X between the two electrodes is 10 mm. The second negative electrode 2 electrodes) were immersed.

これら正電極と第１，第２の負電極間に１５０Ｖの直流電圧を印加し（電流：６Ａ）、被加工材を１m／分で移動させた。そして、第１の負電極が導電性金属酸化物薄膜を通過した後は、前記移動を６０秒間停止して導電性金属酸化物薄膜の最終端部を還元した。   A DC voltage of 150 V was applied between the positive electrode and the first and second negative electrodes (current: 6 A), and the workpiece was moved at 1 m / min. Then, after the first negative electrode passed through the conductive metal oxide thin film, the movement was stopped for 60 seconds to reduce the final end of the conductive metal oxide thin film.

以上の本発明を実施したところ、導電性金属酸化物薄膜の最終端部までＩＴＯが除去でき、ガラス基板の再生が可能になった。   As a result of carrying out the present invention as described above, the ITO can be removed up to the final end of the conductive metal oxide thin film, and the glass substrate can be regenerated.

また、上記実験例の正電極と第１の負電極を被加工物の幅方向に１２分割して千鳥状に配置し、分割した第１の負電極に１個ずつ第２の負電極を設置したほかは、全て上記実験例と同じ条件で実験を行なったところ、導電性金属酸化物薄膜の最終端部までＩＴＯが除去でき、ガラス基板の再生が可能になった。   Further, the positive electrode and the first negative electrode of the above experimental example are divided into 12 in the width direction of the workpiece and arranged in a staggered manner, and the second negative electrode is installed one by one on the divided first negative electrode. In all other cases, the experiment was performed under the same conditions as in the above experimental example. As a result, ITO was removed to the final end of the conductive metal oxide thin film, and the glass substrate could be regenerated.

さらに、上記実験例により除去したＩＴＯを、図１０で説明した回収装置（フィルタのメッシュ：１μm、回収タンク容量：５０リットル、マイクロバブル発生量：２リットル／分、フィルタへの吐出量：１０リットル／分）で回収したところ、ＩｎとＳｎを金属固体として回収できた。なお、フィルタへはマイクロバブルを混入して１分後に吐出を開始した。   Furthermore, the ITO removed in the above experimental example was recovered using the recovery device described in FIG. 10 (filter mesh: 1 μm, recovery tank capacity: 50 liters, microbubble generation amount: 2 liters / minute, discharge amount to the filter: 10 liters). / Min), In and Sn could be recovered as metal solids. In addition, microbubbles were mixed into the filter, and discharge was started 1 minute later.

前記回収金属をＸ線マイクロアナライザーで成分分析したところ、ＩＴＯの成分であるＩｎとＳｎがＩｎ：Ｓｎ＝９：１の割合で検出され、ＩＴＯがそのままの成分比率で回収できたことを確認した。   As a result of component analysis of the recovered metal with an X-ray microanalyzer, In and Sn, which are ITO components, were detected at a ratio of In: Sn = 9: 1, and it was confirmed that ITO was recovered at the same component ratio. .

本発明は、前述の例に限るものではなく、例えば基材や電極を電解液に浸漬させるものに代えて、基材や電極の必要部位に電解液を供給するようにしても良いなど、各請求項に記載の技術的思想の範囲内において、適宜実施の形態を変更しても良いことは言うまでもない。また、電解液１７中に混入する還元金属の回収も図１０に示した方法に限らない。   The present invention is not limited to the above-described example. For example, instead of immersing the base material or the electrode in the electrolytic solution, the electrolytic solution may be supplied to a necessary part of the base material or the electrode. Needless to say, the embodiments may be appropriately changed within the scope of the technical idea described in the claims. Moreover, the collection | recovery of the reduced metal mixed in the electrolyte solution 17 is not restricted to the method shown in FIG.

Claims (7)

基材の表面に形成された導電性金属酸化物薄膜に対向すべく、
正電極と第１の負電極を非接触状態で並列に配置すると共に、前記第１の負電極の前段又は後段、或いは、前段及び後段に、第２の負電極を前記導電性金属酸化物薄膜の幅方向に複数、接触状態で配置した後、
これらの正電極、第１，第２の負電極と前記導電性金属酸化物薄膜間に電解液を介在させた状態で、
前記正電極、第１，第２の負電極に電圧を印加して、
前記正電極、第１，第２の負電極と基材の表面に形成された導電性金属酸化物薄膜とを、導電性金属酸化物薄膜が第１の負電極、第２の負電極を通過後に正電極を通過するように相対移動させることで、前記基材表面の導電性金属酸化物薄膜を還元反応により除去することを特徴とする導電性金属酸化物薄膜の除去方法。To face the conductive metal oxide thin film formed on the surface of the substrate,
The positive electrode and the first negative electrode are arranged in parallel in a non-contact state, and the second negative electrode is placed on the conductive metal oxide thin film before or after the first negative electrode, or before and after the first negative electrode. After arranging a plurality of contacts in the width direction,
In a state where an electrolyte is interposed between the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film,
Apply voltage to the positive electrode, the first and second negative electrodes,
The conductive metal oxide thin film passes through the first negative electrode and the second negative electrode through the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film formed on the surface of the substrate. A method for removing a conductive metal oxide thin film, wherein the conductive metal oxide thin film on the surface of the base material is removed by a reduction reaction by relative movement so as to pass through a positive electrode later. 前記複数配置した第２の負電極間の間隔は、前記正電極と第１の負電極間の間隔以上で、前記正電極と第１の負電極間の間隔の１０倍以下であることを特徴とする請求項１に記載の導電性金属酸化物薄膜の除去方法。   The interval between the plurality of second negative electrodes arranged is not less than the interval between the positive electrode and the first negative electrode and not more than 10 times the interval between the positive electrode and the first negative electrode. The method for removing a conductive metal oxide thin film according to claim 1. 前記の正電極と第１の負電極が、
導電性金属酸化物薄膜の幅よりも狭幅の正電極と第１の負電極を千鳥状に配置したものであることを特徴とする請求項１又は２に記載の導電性金属酸化物薄膜の除去方法。The positive electrode and the first negative electrode are
The conductive metal oxide thin film according to claim 1 or 2, wherein a positive electrode and a first negative electrode narrower than the width of the conductive metal oxide thin film are arranged in a staggered manner. Removal method. 前記電解液は、抵抗率が１０2Ω・cmから１０6Ω・cmのものを使用することを特徴とする請求項１又は２に記載の導電性金属酸化物薄膜の除去方法。The method for removing a conductive metal oxide thin film according to claim 1 or 2, wherein the electrolyte has a resistivity of 10 2 Ω · cm to 10 6 Ω · cm. 前記電解液は、抵抗率が１０2Ω・cmから１０6Ω・cmのものを使用することを特徴とする請求項３に記載の導電性金属酸化物薄膜の除去方法。The method for removing a conductive metal oxide thin film according to claim 3, wherein the electrolytic solution has a resistivity of 10 2 Ω · cm to 10 6 Ω · cm. 請求項１に記載の導電性金属酸化物薄膜の除去方法を実施する装置であって、
基材の表面に形成された導電性金属酸化物薄膜に対向すべく非接触状態で並列に配置された正電極及び第１の負電極と、
前記第１の負電極の前段又は後段、或いは、前段及び後段に、前記導電性金属酸化物薄膜に対向すべく導電性金属酸化物薄膜の幅方向に接触状態で複数配置された第２の負電極と、
これら正電極、第１，第２の負電極と前記基材の表面に形成された導電性金属酸化物薄膜間に電解液を供給する手段、或いは、前記の正電極、第１，第２の負電極と基材を電解液内に浸漬すべく電解液を貯留する電解液槽と、
これらの正電極と第１，第２の負電極に電圧を印加する電源と、
前記正電極、第１，第２の負電極と基材の表面に形成された導電性金属酸化物薄膜とを、導電性金属酸化物薄膜が第１の負電極、第２の負電極を通過後に正電極を通過するように相対移動させる移動機構を備えたことを特徴とする導電性金属酸化物薄膜の除去装置。An apparatus for performing the method for removing a conductive metal oxide thin film according to claim 1,
A positive electrode and a first negative electrode arranged in parallel in a non-contact state to face the conductive metal oxide thin film formed on the surface of the substrate;
A plurality of second negative electrodes arranged in contact with each other in the width direction of the conductive metal oxide thin film so as to face the conductive metal oxide thin film before or after the first negative electrode, or before and after the first negative electrode. Electrodes,
Means for supplying an electrolytic solution between the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film formed on the surface of the substrate, or the positive electrode, the first and second electrodes An electrolytic bath for storing the electrolytic solution so as to immerse the negative electrode and the substrate in the electrolytic solution;
A power source for applying a voltage to the positive electrode and the first and second negative electrodes;
The conductive metal oxide thin film passes through the first negative electrode and the second negative electrode through the positive electrode, the first and second negative electrodes, and the conductive metal oxide thin film formed on the surface of the substrate. An apparatus for removing a conductive metal oxide thin film, comprising a moving mechanism for moving the electrode so as to pass through a positive electrode later. 前記正電極と第１の負電極が、
導電性金属酸化物薄膜の幅よりも狭幅のものを千鳥状に、或いは、導電性金属酸化物薄膜の幅よりも狭幅の湾曲状のものを連続して配置したものであることを特徴とする請求項６に記載の導電性金属酸化物薄膜の除去装置。The positive electrode and the first negative electrode are
One having a narrower width than the width of the conductive metal oxide thin film is arranged in a staggered manner, or one having a curved shape narrower than the width of the conductive metal oxide thin film is continuously arranged. The apparatus for removing a conductive metal oxide thin film according to claim 6.
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